Process for the fixation of mechanically produced effects on textile material, and material



linited States Patent F PROCESS FOR THE FIXATION 0F MECHANI- CALLY PRQDUCED EFFECTS ON TEXTILE MATERIAL, AND MATERIAL Emil Knup, Arlesheim, and Rudolf Aenishaenslin and Gustav Widmer, Basel, Switzerland, assignors to Cilia Limited, Basel, Switzerland, 21 Swiss firm No Drawing. Application February 23, 1954, Serial No. 412,082

Claims priority, application Switzerland February 24, 1953 20 Claims. (Cl. 117-65) It is known that mechanically produced effects on textile fabrics, such as are obtained by calendering, embossing and similar methods can be fixed by means of hardenable artificial resins so as to resist washing. To this end the fabrics are impregnated with aqueous solutions of hardenable condensates of formaldehyde and phenols, urea or related compounds, such as thiourea, dicyandiamide, melamine or other aminotriazines, or mixtures of urea and thiourea, then dried and, after moistening again, that is to say, conditioning, subjected to a mechanical treatment for producing the desired effect, for example in a calendar or similar apparatus and, finally, heated to convert the hardenable condensate into the insoluble state. The use of water-soluble ethers of dimethylolurea and of methylohnelamine has also been recommended for this purpose. In conjunction with these condensates use may be made of hardening catalysts, finishing agents, softeners, matting agents, fillers and other suitable additives..

It has also been recommended to impregnate cellulosic textile material with a neutral aqueous solution of a condensate of formaldehyde and urea or a derivative thereof and, after drying and conditioning, to subject it to a mechanical treatment and then to impregnate or otherwise treat it with a cold, concentrated and acidified solution of a salt which has a strong aifinity for water, but does not specifically cause cellulose to swell, as e. g. the chlorides of calcium, magnesium or aluminum. This procedure makes it possible to avoid high temperatures for the polymerization of the condensate.

Another procedure consisted in filling the interstices of fabrics with easily removable material, such as starch, inv some cases also with hardening catalysts, and passing the fabric through a glazing or similar calender, coating it on one side evenly with a thin layer of hardenable resin, which is cautiously hardened and, after calendering the fabric again, is completely hardened, and crushed after removal of the filling material from the fabric.

Furthermore, it has been proposed to make chintz or fabrics with a chintz dressing by impregnating the fabric with a solution of a urea-formaldehyde condensate and a coagulated protein, and polymerizing the resin simultaneously with the production of a gloss effect by applying sufficient heat and pressure, for example, in a heated calender, or by impregnating the fabric with an aqueous solution of a urea-formaldehyde condensate of -20 per cent strength by weight, drying the condensate at a temperature below its polymerization temperature to a point where it is still moist, and then subjecting it to simultaneous gloss-finishing and hardening at a temperature high enough to bring-about the hardening of the resin, for example in a glazing calender. It has also been proposed to use for the impregnation, solutions of ureaformaldehyde condensates containing a wetting agent,

ice

e. g. sulfonated castor oil and, if necessary, catalysts and/ or softeners.

The present invention, now, is based on the observation that for the fixation of the mechanically produced effects it is of especial advantage to use water-soluble alkyl ethers of such ureau-formaldehyde condensation products as contain per mol of urea more than two mols of formaldehyde, as a rule essentially in the form of methylol groups.

To prepare the products to be used according to this invention more than two mols, preferably between 3 and 5 mols, of formaldehyde are used per mol of urea, the unreacted excess of formaldehyde being distilled oif, if necessary. The condensation of the urea with the formaldehyde is advantageously carried out in an alkaline medium, e. g. at a pH of 75-10. For the etherification of the methylol compounds low molecular, m'onohydric aliphatic alcohols can be used, preferably methanol. The etherification is carried out in the usual manner, advantageously with the use of a small quantity of an acid as catalyst. All of the methylol groups in the condensation products can be etherified. It is however also possible to eifect partial etherification.

The etherified condensation products are oils to vis cous masses which can be stored very well and are readily soluble in water.

In using the etherified condensation products for the fixation of mechanically produced etiects on textile materials, the usual known methods are followed. The ethers to be used for this invention can be hardened with the aid of heat alone. However, it is of advantage to add the customary hardening catalysts. This is of particular advantage in practicing the present process because at ordinary temperature the ethers to be used are unalfected by the acid catalysts, so that solutions with admixed catalysts will keep for several days without undergoing any undesirable changes. The ethers of the condensation products can be used by themselves or together with other auxiliaries, such as coagulatable proteins, dyestuffs, dyestuff components, pigments, softeners or coating agents.

Valuable fixations are obtained with the use, for example, of mixtures of the products of this invention with water-soluble formaldehyde condensation products of other compounds which, together with formaldehyde, yield hardenable aminoplasts, such as guanidine, biuret, dicyandiamide, aminotriazines, such as benzoguanamine, acetoguanamine, formoguanamine or preferably melamine, and also with their water-soluble alkyl ethers and/or water-soluble snythetic polymerization products,

such as polyvinyl alcohol or partially hydrolyzed polyvinyl acetates.

The present process is applicable to all kinds of fibers on which mechanically produced efiects can be fixed with hardenable artificial resins. It is particularly suited for the treatment of fiber material of regenerated cellulose, such as, for example, for the production of chintz effects and embossing effects on fabrics of viscose staple fibers or viscose rayon. The feel of the regenerated cellulose treated according to this process is as a rule agreeably soft and the wash fastness of the effects obtained thereon is quite satisfactory.

Thefollowing examples illustrate the invention, the parts being by Weight unless otherwise stated and the relation between parts by weight'and parts by.volurne being the same as that between the kilogram and the liter.

Example 1 In producing and fixing a chintz eifect the following procedure may be employed. A viscose rayon fabric is impregnated in a foulard with a solution containing, per

liter, 150 grams of the ether described below and grams of tartaric acid or 6 grams of lactic acid. It is squeezed to 180-190 per cent. of its original weight and dried in the usual manner until -15 per cent. of moisture remain in the fabric. When imparting a chintz effect a temperature of 150-180" C. and a working pressure of 100 kg. per centimeter are applied. Curing follows at ISO-160 C. for 5 minutes.

The ehintz effect so obtained is fast to Washing and the viscose rayon has a pleasant feel.

The aforementioned ether can be prepared as follows:

1 mol of urea is condensed at a pH of 8.5 at 95 C. for one hour with 4.5 mols of aqueous formaldehyde. Any excess of aldehyde and the water are then distilled off under reduced pressure. The distillation residue is dissolved in methanol. After the addition of a small quantity of hydrochloric acid, the etherification mixture is allowed to stand at 30-35" C. for minutes, after which the acid is neutralized and the excess of methyl alcohol is distilled off. The residue is a water-soluble, pale syrup.

Example 2 A procedure for the production and fixation of an embossing effect is as follows: A viscose rayon fabric is impregnated in a foulard with a solution containing, per liter, 150 grams of the ether described in Example 1 and 5 grams of tartaric acid or 6 grams of lactic acid, squeezed to 180-190 per cent. of its original weight and dried in the usual manner until 10-15 per cent. of moisture remain in the fabric. Work in the embossing calender is performed at a pressure of 100 kg. per centimeter and at a temperature of ISO-180 C., and the subsequent curing carried out for 5 minutes at ISO-160 C.

The resulting embossing effect is fast to washing and iscose rayon has a pleasant feel.

Example 3 in producing and fixing a chintz effect the following procedure may be employed. A fabric of viscose staple fibers is impregnated in a foulard with a solution containing. per liter, 40 grams of a water-soluble melamine which contains about 2 methylol groups, 40 grams of a watersoluble methylol-melamine which contains about 4 methylol ether groups, 40 grams of the alkyl ether described in Example 1, 15 grams of an aqueous solution of polyvinyl alcohol of per cent. strength by Weight, 10 grams of urea, and 18 grams of a mixture of calcium chloride and boric acid. The fabric is squeezed to 180- 190 per cent. of its dry weight and dried in the usual manner until 10-15 per cent. of moisture remain in the fabric. When imparting a chintz effect a temperature of 150- 180 C. and a working pressure of 100 kg. per centimeter are applied. Curing follows at 150-160" C. for 5 minutes.

The chintz effect so obtained is fast to washing and the viscose rayon has a pleasant feel.

Example 4 A procedure for the production and fixation of an embossing effect is as follows: A viscose rayon fabric is impregnated in a foulard with a solution containing, per liter, grams of a water-soluble melamine which contains about 2 methylol groups, 40 grams of a water-soluble rmthylol-melamine which contains about 4 methylol other groups, 40 grams of the alkyl ether described in Example 1. 15 grams of an aqueous solution of polyvinyl alcohol of 20 per cent. strength by weight, 10 grams of urea and 18 grams of a mixture of calcium chloride and boric acid. The fabric is squeezed to 180-190 per cent. of its dry weight and dried in the usual manner until 10-15 per cent. of moisture remain in the fabric. Work in the embossing calender is performed at a pressure of 100 kg. per centimeter and at. a temperature of ISO-180 C. and the subsequent curing carried out for 5 minutes at 150-160" C.

The resulting embossing effect is fast to washing and the viscose rayon has a pleasant feel.

What is claimed is:

1. In the process for the wash-resisting fixation of effects on cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble alkyl ether of such a ureaformaidehydc condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups.

2. in the process for the wash-resisting fixation of effects on cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups.

in the process for the wash-resisting fixation of effects on cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble alkyl ether of such a ureaformaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with at least one melamine-formaldehyde condensation product of the group consisting of a water-soluble mclamine-formaldehyde condensation product and a water-soluble alkyl ether thereof.

4. In the process for the wash-resisting fixation of effects on cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble alkyl ether of such a ureaformaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with at least one melamine-formaldehyde condensation product of the group consisting of a water-soluble melamine-formaldehyde condensation product and a water-soluble alkyl ether thereof and also in admixture with polyvinyl alcohol.

5. In the process for the wash-resisting fixation of effects on regenerated cellulosecontaining textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble alkyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups.

6. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile ma terial by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups.

7. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble alkyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with at least one melamineformaldehyde condensation product of the group consisting of a water-soluble melamine-formaldehyde condensation product and a water-soluble alkyl ether thereof.

8. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with at least one melamineformaldehyde condensation product of the group consisting of a water-soluble melamine-formaldehyde condensation product and a Water-soluble alkyl ether thereof.

9. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble alkyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with a water-soluble melarninc-formaldehyde-condensation product containing about 2 methylol groups and with a Water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4 methoxymethyl groups.

10. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble alkyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with a water-soluble melamine-formaldehyde-condensation product containing about 2 methylol groups and with a watersoluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4 methoxy-rnethyl groups and also with polyvinyl alcohol.

11-. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble alkyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said other being in admixture with a water-soluble melamineformaldehyde-condensation product containing about 2 methylol groups and with a water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4-methoxy-methyl groups and also with a partially hydrolized polyvinyl acetate.

12. In the process for the wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the ureaformaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with a Water-soluble melamineformaldehyde-condensation product containing about 2 methylol groups and with a water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4 methoxy-methyl groups.

13. In the process for the Wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with a water-soluble melamine-formaldehydecondensation product containing about 2 methylol groups and With a water-soluble methyl ether of a melamine formaldehyde condensation product, said methyl ether containing about 4 methoxy-methyl groups and also with polyvinyl alochol.

14. In the process for the Wash-resisting fixation of effects on regenerated cellulose-containing textile material by subjecting the textile material impregnated with an aqueous solution of a hardenable urea-formaldehyde condensation product to a treatment in a mechanical finishing machine and thereafter heat hardening the condensation product, the improvement that the urea-formaldehyde condensation product is a water-soluble methyl ether of such a urea-formaldehyde condensation product as contains, per mol urea, more than 2 mols formaldehyde essentially in the form of methylol groups, said ether being in admixture with a water-soluble melamineformaldehyde-condensation product containing about 2 methylol groups and with a water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4-methoxy-methyl groups and also with a partially hydrolized polyvinyl acetate.

15 A cellulose-containing textile material with effects produced by means of a mechanical finishing machine and fixed with a hardened alkyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups.

16. A cellulose-containing textile material with effects produced by means of a mechanical finishing machine and fixed with a hardened methyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups.

17. A cellulose-containing textile material with effects produced by means of a mechanical finishing machine and fixed with a hardened alkyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups, said ether being hardened in admixture with at least one melamine-formaldehyde condensation product of the group consisting of a water-soluble melamine-formaldehyde condensation product and a Water-soluble alkyl ether thereof.

18. A regenerated cellulose-containing textile material with effects produced by means of a mechanical finishing machine and fixed with a hardened methyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups, said ether being hardened in admixture with a water-soluble melamine-formaldehyde-condensation product containing about 2 methylol groups and with a water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4-1nethoxy-methyl groups.

19. A regenerated cellulosecontaining textile material with effects produced by means of a mechanical finishing machine and fixed with a hardened methyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups, said ether being hardened in admixture with a water-soluble melamine-formaldehyde-condensation product containing about 2 methylol groups and with a water-soluble methyl ether of a melamine-formaldehyde condensation product, said methyl ether containing about 4-inethoxy-methyl groups and also with polyvinyl alcohol.

20. A regenerated cellulose-containing textile material with efiects produced by means of a mechanical finishing machine and fixed with a hardened methyl ether of a urea formaldehyde condensation product containing per mol of urea more than 2 mols of formaldehyde essentially in the form of methylol groups, said ether being hardened in admixture with a water-soluble melamine-formaldehyde-condensation product containing about 2 methylol groups and with a watensoluble methyl ether of a melamineforrnaldehyde condensation product, said methyl ether containing about 4-rnethoxy-methyl groups, and also with a partially hydrolized polyvinyl acetate.

References Cited in the file of this patent UNITED STATES PATENTS 2,469,408 Power's May 10, 1949 2,498,454 Schibler Feb. 2, 1950 2,577,957 Farnsworth Dec. 11, 1951 2,622,995 Lippert et al. Dec. 23, 1952 FOREIGN PATENTS 608,487 Great Britain of 1948 

1. IN THE PROCESS FOR THE WASH-RESISTING FIXATION OF EFFECTS OF CELLULOSE-CONTAINING TEXTILE MATERIAL BY SUBJECTING THE TEXTILE MATERIAL IMPREGNATED WITH AN AQUEOUS SOLUTION OF A HARDENABLE UREA-FORMALDEHYDE CONDENSATION PRODUCT TO A TREATMENT IN A MECHANICAL FINISHING MACHINE AND THEREAFTER HEAT HARDENING THE CONDENSATION PRODUCT, THE IMPROVEMENT THAT THE UREA-FORMALDEHYDE CONDENSATION PRODUCT IS A WATER-SOLUBLE ALKYL ETHER OF SUCH A UREAFORMALDEHYDE CONDENSATION PRODUCT AS CONTAINS, PER MOL UREA, MORE THAN 2 MOLS FORMALDEHYDE ESSENTIALLY IN THE FORM OF METHYLOL GROUPS. 